CN106662415A

CN106662415A - Heat exchanger including fins with surface having bactericidal activity, metallic member with surface having bactericidal activity, method for inhibiting mold growth and sterilization method both using surface of fins of heat exchanger or surface of metallic member, and electrical water boiler, beverage supplier, and lunch box lid all including metallic member

Info

Publication number: CN106662415A
Application number: CN201580042562.5A
Authority: CN
Inventors: 山田美穗; 箕浦洁; 中原隆裕; 楠本晃司
Original assignee: Sharp Corp
Current assignee: Sharp Corp
Priority date: 2014-08-07
Filing date: 2015-07-10
Publication date: 2017-05-10
Anticipated expiration: 2035-07-10
Also published as: US11280563B2; US20170227305A1; JP6543311B2; CN106662415B; CN109059605B; JP6726335B2; US10107574B2; JP2019150626A; TWI670463B; TWI629445B; US20180252484A1; JP6215476B2; WO2016021367A1; TW201612487A; JPWO2016021367A1; JP2018028148A; TW201829974A; CN109059605A

Abstract

A heat exchanger including fins (50) which each comprise a metallic base (18Xr) and a porous anodized layer (14) formed on the metallic base (18Xr), the surface of the porous anodized layer having a submicrometer-odor rugged structure, which includes a plurality of recesses (14Ap) or (14Bp) that, when viewed from the direction normal to the surface, has a two-dimensional size greater than 100 nm but less than 500 nm.

Description

Possess the heat exchanger of the fin of bactericidal action with surface, with possessing sterilization The hardware on the surface of effect, using heat exchanger fin surface or The surface of hardware suppresses the method and method for disinfection of mould generation and has The electric heater of hardware, beverage supply device and cover of the lunch box

Technical field

The present invention relates to possess the heat exchanger of the fin of bactericidal action with surface, with the table for possessing bactericidal action The hardware in face, using heat exchanger fin surface or hardware surface suppress mould occur method and Method for disinfection and the electric heater with hardware, beverage supply device and cover of the lunch box.

Background technology

Recently, the article that the nano surface structure that the wing of black silicon, cicada or dragonfly has has bactericidal action has been delivered (non-patent literature 1).The nano-pillar that black silicon has height for 500nm is for example pointed out, the physical arrangement of the nano-pillar can show Bactericidal action.The wing of cicada or dragonfly has nano-pillar of the height for 240nm.

According to non-patent literature 1, bactericidal action of the black silicon to Gram-negative bacteria is most strong, the wing of dragonfly, cicada Wing is weaker successively.In addition, their surface to the static contact angle of water (below, sometimes referred to simply as " contact angle ".) be：Black silicon For 80 °, and the wing of dragonfly is 153 °, and the wing of cicada is 159 °.

Prior art literature

Patent document

Patent document 1：Specially permit No. 4265729 publication

Patent document 2：JP 2009-166502 publication

Patent document 3：International Publication No. 2011/125486

Patent document 4：International Publication No. 2013/183576

Patent document 5：JP 2010-175131 publication

Non-patent literature

Non-patent literature 1：Ivanova, E.P.et al., " Bactericidal activity of black Silicon ", Nat.Commun.4：2838doi：10.1038/ncomms3838(2013).

The content of the invention

Problems to be solved by the invention

From the point of view of the result described in non-patent literature 1, the mechanism for killing bacterium by nano-pillar is unclear.And, Unclear black silicon have the bactericidal action stronger than the wing of dragonfly, cicada the reason for be nano-pillar height or shape not Together, still it is the difference of surface free energy (can be evaluated with contact angle).In addition, not knowing bactericidal action whether according to tool yet There is the material (black silicon and other materials (such as metal)) of nano-pillar and change.

And, even if to utilize the bactericidal action of black silicon, because black silicon production is poor and hard and crisp, there is also shape processing The low problem of property.

The present invention is completed to solve the problems, such as above-mentioned, its main purpose is, provide to possess with surface killing The heat exchanger of fin of bacterium effect, the hardware with the surface for possessing bactericidal action, using the radiating of heat exchanger The surface of piece or the surface of hardware suppress the method and method for disinfection and the electric heating with hardware of mould generation Hydrophone, beverage supply device and cover of the lunch box.

For solution to problem

The heat exchanger of embodiments of the present invention has fin, and above-mentioned fin has metal base and is formed in The porous anode layer on metal base is stated, the surface of above-mentioned porous anode layer has the concavo-convex knot of sub-micrometer scale Structure, above-mentioned concaveconvex structure includes that from above-mentioned normal to a surface direction two-dimentional size when watching is more than 100nm and less than 500nm's Multiple recesses.

In certain embodiment, above-mentioned concaveconvex structure has the jut being formed between adjacent above-mentioned multiple recesses.

In certain embodiment, the rib that above-mentioned jut has the side of adjacent above-mentioned multiple recesses intersecting and formed Line.

In certain embodiment, the adjacent spacing of above-mentioned multiple recesses is more than the above-mentioned two-dimentional size of above-mentioned multiple recesses.

In certain embodiment, the side of above-mentioned multiple recesses is inclined relative to above-mentioned normal to a surface direction.

In certain embodiment, at least a portion of the side of above-mentioned multiple recesses is step-like.

In certain embodiment, above-mentioned surface is less than 110.4 ° to the static contact angle of hexadecane.

In certain embodiment, above-mentioned surface is less than 29.3 ° to the static contact angle of hexadecane.

In certain embodiment, above-mentioned surface was processed with surface conditioning agent.

In certain embodiment, above-mentioned surface conditioning agent has amino.

In certain embodiment, the adjacent spacing of above-mentioned multiple recesses is more than 20nm and less than 500nm.

In certain embodiment, the above-mentioned two-dimentional size of above-mentioned multiple recesses is more than 140nm.

In certain embodiment, above-mentioned metal base is valve metal.

In certain embodiment, above-mentioned porous anode layer is formed by carrying out anodic oxidation to valve metal.

The hardware of embodiments of the present invention possesses metal base and the porous sun being formed on above-mentioned metal base Pole oxide layer, the surface of above-mentioned porous anode layer has the concaveconvex structure of sub-micrometer scale, and above-mentioned surface has sterilized effect Really.

In certain embodiment, above-mentioned concaveconvex structure includes that from above-mentioned normal to a surface direction two-dimentional size when watching is Multiple recesses more than 100nm and less than 500nm.

The method that mould occurs that suppresses of embodiments of the present invention is to make vapor with any of the above-described heat exchanger The above-mentioned surface contact of above-mentioned fin.

Embodiments of the present invention gas or liquid are carried out sterilization method be make gas or liquid with it is above-mentioned The above-mentioned surface contact of the above-mentioned fin of any one heat exchanger.

The method that mould occurs that suppresses of another embodiment of the present invention is to make vapor with any of the above-described metal structure The above-mentioned surface contact of part.

The method that sterilization is carried out to gas or liquid of another embodiment of the present invention be make gas or liquid with The above-mentioned surface contact of any of the above-described hardware.

The electric heater of embodiments of the present invention has：Container, it accommodates drinking water, and what heating was accommodated above-mentioned drinks Water；Outlet, it is by heated above-mentioned drinking water to outside discharge；And drinking-water pipe, it is located at said vesse with above-mentioned row Between outlet, above-mentioned drinking-water pipe has metal base and the porous anode layer being formed on above-mentioned metal base in inner side, The surface of above-mentioned porous anode layer has the concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure is included from above-mentioned surface Two-dimentional size when normal direction is watched is the multiple recesses more than 100nm and less than 500nm.Above-mentioned electric heater is, for example, electricity Hot-water bottle.

The beverage supply utensil of embodiments of the present invention has：Container, it accommodates drinking water, heats the above-mentioned drink for being accommodated Use water；Outlet, it will be discharged including the beverage of heated above-mentioned drinking water to outside；And feed pipe, it is located at above-mentioned Between container and above-mentioned outlet, above-mentioned feed pipe has metal base and the porous being formed on above-mentioned metal base in inner side Anodic oxide coating, the surface of above-mentioned porous anode layer has the concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure includes Two-dimentional size when watching from above-mentioned normal to a surface direction is the multiple recesses more than 100nm and less than 500nm.Above-mentioned beverage Supply is, for example, coffee machine.

The cover of the lunch box of embodiments of the present invention has metal base and the porous anode being formed on above-mentioned metal base Oxide layer, the surface of above-mentioned porous anode layer has a concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure is included from upper It is the multiple recesses more than 100nm and less than 500nm to state two-dimentional size when normal to a surface direction is watched.

Invention effect

According to the embodiment of the present invention, heat exchanger, the tool of the fin for possessing bactericidal action with surface can be provided There is the hardware on the surface for possessing bactericidal action, pressed down using the surface of fin or the surface of hardware of heat exchanger Method and method for disinfection and the electric heater with hardware, beverage supply device and cover of the lunch box that mildew making occurs.

Description of the drawings

Fig. 1 (a) is the schematic sectional view of the hardware 100A of embodiments of the present invention, (b) is the another of the present invention The schematic sectional view of the hardware 100B of one embodiment.

Fig. 2 (a) is of the schematic perspective view of hardware 100A, (b) is schematically bowing for hardware 100A One of view.

Fig. 3 (a) is of the schematic plan of hardware 100A, (b) is the 3B-3B ' lines along in (a) One of the schematic sectional view of hardware 100A, is (c) that the hardware 100A of 3C-3C ' lines along in (a) shows One of meaning property sectional view.

Fig. 4 (a)～(e) is the figure of the structure of the manufacture method for illustrating hardware 100A and hardware 100A.

Fig. 5 (a)～(c) is the figure of the structure of the manufacture method for illustrating hardware 100B and hardware 100B.

Fig. 6 (a) is the schematic sectional view of the hardware 100A ' of another embodiment of the invention, (b) is the present invention Another embodiment hardware 100B ' schematic sectional view, be (c) for illustrating hardware 100A ' and metal The schematic figure of the manufacture method of component 100B '.

Fig. 7 (a) is the SEM pictures on the surface that the 3rd sample is observed with SEM (scanning electron microscope), (b) is seen with SEM Examine the SEM pictures in the section of the 3rd sample.

Fig. 8 is to represent the bacterium number (CFU/mL) in the bacterium dilution B relative to the elapsed time (h) in the 1st～the 4th sample Coordinate diagram.

Fig. 9 (a) is the SEM pictures on the surface for observing the 5th sample from the angle that normal to a surface direction inclines 45 ° with SEM, B () is the SEM pictures on the surface for observing the 6th sample from the angle that normal to a surface direction inclines 45 ° with SEM, be (c) to represent the 5th The coordinate diagram of the bacterium number (CFU/mL) in the bacterium dilution B relative to the elapsed time (h) of the～the 7 sample, is (d) to represent the 8th The coordinate diagram of the bacterium number (CFU/mL) in the bacterium dilution B relative to the elapsed time (h) of the～the 9 sample.

Figure 10 is the figure of the SEM pictures for representing the surface for becoming transparent position that the 13rd sample is observed with SEM.

Figure 11 (a) is the schematic sectional view of the fin 50 that the heat exchanger of embodiments of the present invention has, and (b) is The schematic sectional view of the heat exchanger 200A of embodiments of the present invention, is (c) that the hot of another embodiment of the present invention is handed over The schematic sectional view of parallel operation 200B.

Figure 12 (a) is the schematic plan of the radiator 210A of embodiments of the present invention, is (b) respectively edge with (c) The sectional view of the radiator 210A of 12B-12B ' lines in (a) and 12C-12C ' lines.D () is another embodiment party of the present invention The schematic plan of the radiator 210B of formula, (e) with (f) respectively along the 12E-12E ' lines and 12F-12F ' in (d) The sectional view of the radiator 210B of line.

Figure 13 is to schematically show the chair 60A manufactured using the interior decoration building materials of embodiments of the present invention Figure.

Figure 14 (a) is the sectional view of the electric heater 70A for schematically showing embodiments of the present invention, (b) is to illustrate Property ground represent another embodiment of the present invention electric heater 70B sectional view.

Figure 15 is the sectional view of the beverage supply device 80 for schematically showing embodiments of the present invention.

Figure 16 is the figure of the lunch box 90a and cover of the lunch box 90b that schematically show embodiments of the present invention.

Specific embodiment

The hardware and heat exchanger of embodiments of the present invention are illustrated referring to the drawings.Additionally, the present invention is not limited In the embodiment of the example below.In figures in the following, the substantially inscape with identical function is with common accompanying drawing Mark illustrates that sometimes the description thereof will be omitted.

Additionally, in this manual, using following term.

" sterilized (sterilization (microbicidal)) " is to instigate object or limited as object, liquid The effective quantity of fertile microorganism (microorganism) that included of space reduce.

" microorganism " includes virus, bacterium (bacteria), fungi (mould).

" antibacterial (antimicrobial) " extensive suppression comprising to microbial reproduction/prevent, comprising to being led by microorganism The blackspot of cause, the suppression of mucus.

Applicant of the present invention have developed and use to manufacture the antireflection film (antireflective surfaces) with moth ocular structure There is the method (such as patent document 1～4) of the anodic oxidation porous alumina layer of the moth ocular structure of reversion on surface.In order to join Examine, the complete disclosure of patent document 1～4 is quoted in this manual.

The present inventor is by using above-mentioned technology, have developed the metal structure on the surface for possessing bactericidal action Part and possess with surface bactericidal action fin (fin) heat exchanger.

The structure of the hardware of embodiments of the present invention is illustrated with reference to Fig. 1, Fig. 2 and Fig. 3.Fig. 1 (a) represents the present invention Embodiment hardware 100A schematic sectional view.Fig. 1 (b) represents the metal structure of another embodiment of the present invention The schematic sectional view of part 100B.Fig. 2 (a) and Fig. 2 (b) represent respectively the schematic perspective view and top view of hardware 100A One.Fig. 3 (a) represents of the schematic plan of hardware 100A.Fig. 3 (b) is represented along in Fig. 3 (a) One of the schematic sectional view of the hardware 100A of 3B-3B ' lines.Fig. 3 (c) is represented along the 3C-3C ' lines in Fig. 3 (a) One of schematic sectional view of hardware 100A.

As shown in Fig. 1 (a), hardware 100A possesses metal base 12 and the porous anode being formed on metal base 12 Oxide layer 14.The surface of porous anode layer 14 has the concaveconvex structure of sub-micrometer scale.The table of porous anode layer 14 Face has bactericidal effect.There is bactericidal effect this point with regard to the hardware of embodiments of the present invention, will illustrate later Experimental example.

The concaveconvex structure on the surface of porous anode layer 14 for example includes multiple recess 14Ap.As exemplified by Fig. 1 (a) , (such as Fig. 2 (a) and Fig. 2 (b) is shown to there is no gap between adjacent recess 14Ap in recess 14Ap close-packed arrays Example, the bottom surface portions of circular cone ground is overlapped) in the case of, two-dimentional size Dp of recess 14Ap and the adjacent spacing of recess 14Ap Dint is equal.Here, " the two-dimentional size " of recess 14Ap refers to from normal to a surface direction the face with recess 14Ap when watching The suitable diameter of a circle of product.For example in the case where recess 14Ap is cone, the two-dimentional sizableness of recess 14Ap is in circular cone Bottom surface diameter.Two-dimentional size Dp of recess 14Ap is for example, more than 100nm and less than 500nm.In addition, the phase of recess 14Ap Adjacent space D int is for example, more than 20nm and less than 500nm.The typical depth of recess 14Ap be 50nm less than 1000nm。

Hardware 100A can also have the inorganic material layer 16 being formed on metal base 12.Hardware 100A can There is metal remnant layer 18r with 14 times also in porous anode layer.

As exemplified by Fig. 2 (a) and Fig. 2 (b), in the case where recess 14Ap is for cone, the bottom surface of circular cone can be with portion Ground is divided to overlap.Crest line 14r can be formed between adjacent recess 14Ap.Crest line 14r be, for example, adjacent recess 14Ap it is intersecting and Formed.For example in the case where recess 14Ap is for cone, the side of circular cone is intersected, so as to form crest line 14r.Such as Fig. 2 Exemplified by (b), when watching from the normal to a surface direction of porous anode layer 14, match somebody with somebody in the center 14o of recess 14Ap In the case of being set to positive triangular lattice shape, crest line 14r is formed as the regular hexagon centered on the 14o of center.And, equivalent to The position on orthohexagonal summit, can form pointed projections 14c.To claim including crest line 14r and the part including pointed projections 14c For jut 15.Pointed projections 14c more projection compared with crest line 14r, thus the top of jut 15 can be multiple points (for example Pointed projections 14c).The top of so-called jut 15 is, for example, the top on the normal to a surface direction of porous anode layer 14 End.Think hardware 100A by the way that there is jut 15 so as to bactericidal action on surface.

The circle being represented by dashed line in Fig. 2 (a) and Fig. 2 (b) is centered on the center 14o of recess 14Ap and through suitable The circle of pointed projections 14c formed in the position on orthohexagonal summit.Sometimes the diameter of a circle is referred to as into the " empty of recess 14Ap Intend diameter Dhd ".In the case of example in Fig. 2 (a) and Fig. 2 (b), virtual diameter Dhd of recess 14Ap is more than adjacent spacing Dint and two-dimentional size Dp (Dhd ＞ Dint=Dp).

As exemplified by Fig. 3 (a), in the case where recess 14Ap is for cone, the bottom surface of circular cone mutually can also not weigh It is folded.As exemplified by Fig. 3 (a), the fenestra of the bottom surface of circular cone can be mutually tangent.In this case, in adjacent recess 14Ap Between can not form crest line 14r.As exemplified by Fig. 3 (a), seeing from the normal to a surface direction of porous anode layer 14 When seeing, such as in the case that the center 14o in recess 14Ap is configured to positive triangular lattice shape, jut 15 is included equivalent to in The point 14c on the orthohexagonal summit centered on heart 14o and raised areas 14c surrounded by point 14c '.Raised areas 14c ' example It is the region for not forming recess 14Ap when such as watching from normal to a surface direction.

As shown in Fig. 3 (b), in the section along 3B-3B ' lines in Fig. 3 (a), point 14c become be formed at it is adjacent Pointed projections 14c between recess 14Ap.As shown in Fig. 3 (c), in along the section of the 3C-3C ' lines in Fig. 3 (a), projection Region 14c ' is than point 14c more projections.The top of jut 15 in this case is not for example point but multiple regions (such as projection Region 14c ').The top of jut 15 for example can have and raised areas 14c ' identical two dimension size.Raised areas 14c ' Two-dimentional size refer to from normal to a surface direction when watching with raised areas 14c ' the suitable diameter of a circle of area.Projection area Domain 14c ' is formed between the recess 14Ap of sub-micrometer scale, therefore the two-dimentional size on the top of jut 15 can be hundreds of receiving Below rice magnitude.Thus, jut 15 can have bactericidal properties.

In the case where Fig. 3 (a)～(c) is exemplified, virtual diameter Dhd of recess 14Ap and adjacent space D int and two dimension Size Dp equal (Dhd=Dint=Dp).From the physical arrangement on surface there is the viewpoint of excellent bactericidal action to think, such as Fig. 2 A exemplified by () and Fig. 2 (b), virtual diameter Dhd of preferred recess 14Ap is more than adjacent space D int and two-dimentional size Dp (Dhd ＞ Dint=Dp).Its reason is that jut 15 has pointed projections 14c, and the top of jut can become a little.But, it is believed that no Only it is the physical arrangement on surface, the chemical property (such as lipophile) on surface also contributes to the bactericidal action that hardware has. That is, as described in experimental example shown behind, it is also possible to give surface conditioning agent to the surface of porous anode layer 14.At surface Reason agent for example includes releasing agent, silane coupler, hydrophilic coating, anticorrosive etc..By giving surface conditioning agent to surface, The hydrophily and/or lipophile on the surface of adjustable hardware.For example the surface of porous anode layer 14 is to hexadecane Static contact angle both can be less than 110.4 °, and can also be less than 29.3 °.Alternatively, it is also possible to porous anode The surface of layer 14 gives Kang Jun Tu material.By giving Kang Jun Tu material to surface, bactericidal action is can further improve.

The configuration of recess 14Ap is not limited to the configuration exemplified by Fig. 2 and Fig. 3, both can be with rule configuration, it is also possible to irregular (random) configuration.

Then, the hardware 100B of another embodiment of the present invention is illustrated with reference to Fig. 1 (b).Gold shown in Fig. 1 (b) Metal elements 100B is that the concaveconvex structure on the surface of porous anode layer 14 is including more with the difference of hardware 100A Individual recess 14Bp.Hardware 100B can be identical with hardware 100A in addition to multiple recess 14Bp.

As shown in Fig. 1 (b), adjacent space D int of recess 14Bp is more than two-dimentional size Dp (the Dint ＞ of recess 14Bp Dp).Virtual diameter Dhd of recess 14Bp is equal with two-dimentional size Dp of recess 14Bp (Dp=Dhd).In this case, it is adjacent Recess 14Bp it is non-intersect, therefore do not form crest line 14r between adjacent recess 14Bp.The table of porous anode layer 14 Top in the normal direction in face spreads wherein multiple recess 14Bp for example formed as face.To have hardware 100B Bactericidal properties, for example, recess 14Bp two-dimentional size Dp with the relation of adjacent space D int of recess 14Bp, preferably make (Dint-Dp)/Dint is less than 0.9 (that is, Dp/Dint is more than 0.1).There is bactericidal properties, example to make hardware 100B Such as, the surface of preferred porous anode layer 14 carried out surface treatment.Such as surface pair of porous anode layer 14 The static contact angle of hexadecane is less than 110.4 °.It is highly preferred that static state of the surface of porous anode layer 14 to hexadecane Contact angle can be less than 29.3 °.

The manufacture method of the hardware 100A and 100B of embodiments of the present invention is, for example, example shown below, can be helped With the manufacture method for making the mould of antireflection film described in patent document 2～4.Thus, energy precision is advantageously controlled The size and depth of recess.In addition, the recess that can be equably configured.But, in order that with the bactericidal action on surface, should not Ask such as to the high uniformity of antireflection film requirement, therefore the manufacture method of mould can be simplified.For example, as reference Fig. 6 is described later Hardware 100A ' and 100B ' like that, directly can carry out anodic oxygen to the surface of metal base (such as being formed by valve metal) Change to manufacture.

The manufacture method of hardware 100A is illustrated with reference to Fig. 4 (a)～Fig. 4 (e).

First, as shown in Fig. 4 (a), as mould base material mould base material 10 is prepared, mould base material 10 has：Metal Substrate Material 12；It is formed at the inorganic material layer 16 on the surface of metal base 12；And the metal film 18 being deposited on inorganic material layer 16.

Metal base 12 is, for example, aluminium base.Metal film 18 is, for example, aluminium film.Hereinafter illustrate aluminium base 12 and aluminium film 18 Example.Wherein, the hardware not limited to this of embodiments of the present invention.Metal base 12 and metal film 18 are for example respectively by valve Metal is formed.Valve metal be can anodized metal general name, in addition to aluminum, also including tantalum (Ta), niobium (Nb), Mo (molybdenum), titanium (Ti), hafnium (Hf), zirconium (Zr), zinc (Zn), tungsten (W), bismuth (Bi), antimony (Sb).Valve metal is carried out with known method Anodic oxidation.The conditions such as the species or voltage of electrolyte can be suitably selected, set according to each metal.In addition, also dependent on each Individual metal is selecting the etching solution of anode oxide film.For example can the mixed aqueous solution of ethylene glycol and ammonium fluoride, comprising sulfuric acid and/ Or for example anodic oxidation is carried out to Ti in the electrolyte such as phosphorus aqueous acid.As the etching solution of Ti, for example can using include from Including the aqueous acid or fluoric acid mixed aqueous solution (such as fluorine that select in SPA, hot concentrated sulfuric acid, the group of Thickish hot hydrochloric acid Acid/nitric acid mixed aqueous solution, fluoric acid/hydrogen peroxide mixed aqueous solution, ammonium fluoride/fluoric acid mixed aqueous solution etc.).

Metal base 12 and metal film 18 for example can be formed respectively by stainless steel.Although known stainless steel is not belonging to valve gold Category, but the self-organizing structures of sub-micrometer scale can be formed by anodic oxidation.For example in K.Kure et al., “Formation of self-organized nanoporous anodic film on Type 304stainless The stainless steel using 304 types has been recorded in the 1-4. of steel ", Electrochemistry Communications 21 (2012) Form the anode oxide film of the recess with sub-micrometer scale.In order to refer to, all public of the document is quoted in this manual Open content.Additionally, as stainless etching solution, can be using such as chloroazotic acid (by concentrated hydrochloric acid and red fuming nitric acid (RFNA) by volume 3：1 mixing Liquid) etc..

Metal base 12 and metal film 18 can respectively include the high metal of antibacterial effect (such as golden (Au), silver-colored (Ag), platinum Golden (Pt) or copper (Cu)).Metal base 12 and metal film 18 can also be formed by identical metal.For example metal film 18 by In the case that titanium is formed, porous anode layer 14 is formed by titanium oxide.Titanium oxide is photocatalytic substance, therefore metal structure Part also can have based on light-catalysed bactericidal action by illuminated light.

The use of the purity of aluminium is that 99.50 mass % compare less than the rigidity of 99.99 mass % as aluminium base 12 High aluminium base.As the impurity that aluminium base 12 is included, preferably comprise from including iron (Fe), silicon (Si), copper (Cu), manganese (Mn), at least a kind element selected in the group of zinc (Zn), nickel (Ni), titanium (Ti), lead (Pb), tin (Sn) and magnesium (Mg), especially excellent Select Mg.The formation mechenism of the pit (depression) in etching work procedure be local cell reaction, accordingly, it would be desirable to completely do not include than The expensive element of aluminium, preferably uses comprising the Mg (standard electrode potential is -2.36V) as base metal as the aluminium base of impurity element Material 12.If the containing ratio of the element more expensive than aluminium is below 10ppm, from from the viewpoint of electrochemistry, it is possible to say substantially The element is not included.It is preferred that the containing ratio of Mg is more than 0.1 overall mass %, the model below even more preferably about 3.0 mass % Enclose.If the containing ratio of Mg is less than 0.1 mass %, enough rigidity cannot be obtained.On the other hand, if containing ratio is big, easily There is the segregation of Mg.Even if there occurs segregation in the near surface for forming the ophthalmically acceptable mould of moth, will not also become in electrochemistry and ask Topic, but Mg can form the anode oxide film with aluminium different shape, thus the reason for can become bad.The containing ratio of impurity element is only Will be according to the shape of aluminium base 12, thickness and size, according to the required appropriate setting of rigidity.For example added by rolling In the case that work makes the aluminium base 12 of tabular, it is appropriate that the containing ratio of Mg is for about 3.0 mass %, by extrusion process system In the case of making to have the aluminium bases 12 of stereochemical structure such as cylinder, the containing ratio of preferred Mg is below 2.0 mass %.If Mg's contains There is rate more than 2.0 mass %, press workability typically can decline.

As aluminium base 12, for example, use by JIS A1050, Al-Mg systems alloy (such as JIS A5052) or Al-Mg- The cylindric aluminum pipe that Si systems alloy (such as JIS A6063) is formed.

Implement lathe tool cutting in the surface of preferred pair aluminium base 12.When remaining such as abrasive particle on the surface of aluminium base 12 When, it is easy to turn between the part that there is abrasive particle, aluminium film 18 and aluminium base 12.Also there is concavo-convex portion in addition to abrasive particle Point, locally it is easy to turn between aluminium film 18 and aluminium base 12.When locally turning between aluminium film 18 and aluminium base 12, it is possible to Locally there is cell reaction between impurity and aluminium film 18 in aluminium base 12.

As the material of inorganic material layer 16, such as tantalum oxide (Ta can be used₂O₅) or silica (SiO₂).It is inorganic Material layer 16 can be formed for example, by sputtering method.In the case of using tantalum oxide layers as inorganic material layer 16, tantalum oxide layers Thickness be, for example, 200nm.

It is preferred that the thickness of inorganic material layer 16 be 100nm less than 500nm.If the thickness of inorganic material layer 16 is less than 100nm, then sometimes aluminium film 18 can produce defect (mainly space, i.e., intercrystalline gap).If in addition, inorganic material layer 16 Thickness is more than 500nm, then according to the surface state of aluminium base 12, easily insulate between aluminium base 12 and aluminium film 18.In order to logical Cross from the side of aluminium base 12 to aluminium film 18 for induced current to carry out the anodic oxidation of aluminium film 18, need between aluminium base 12 and aluminium film 18 Flow through electric current.When the composition of induced current is supplied using the inner face from cylindric aluminium base 12, electricity need not be set in aluminium film 18 Pole, accordingly, it is capable to carry out to aluminium film 18 anodic oxidation in entire surface, and is also not in difficult with anodised carrying out For the problem of induced current, equably anodic oxidation can be carried out to aluminium film 18 in entire surface.

In addition, the inorganic material layer 16 in order to form thickness, generally requiring makes film formation time elongated.When film formation time it is elongated When, the surface temperature of aluminium base 12 can unnecessarily rise, as a result, the film quality of aluminium film 18 deteriorates, defect be produced sometimes (mainly space).If the thickness of inorganic material layer 16 is less than 500nm, can also suppress the generation of this problem.

Such as described in patent document 3, it with purity is film that more than 99.99 mass % aluminium is formed that aluminium film 18 is (below, sometimes referred to as " high-purity aluminium film ".).Aluminium film 18 is for example formed using vacuum vapour deposition or sputtering method.It is preferred that aluminium Scope of the thickness of film 18 in about more than 500nm and about below 1500nm, e.g. about 1 μm.

In addition, as aluminium film 18, it is also possible to do not use high-purity aluminium film, and use the aluminium alloy described in patent document 4 Film.Aluminium alloy film described in patent document 4 includes the metallic element and nitrogen beyond aluminium, aluminium.In this manual, " aluminium film " High-purity aluminium film is not only included, also comprising the aluminium alloy film described in patent document 4.

When using above-mentioned aluminium alloy film, the minute surface that reflectivity is more than 80% can be obtained.Constitute the crystal grain of aluminium alloy film From the normal direction of aluminium alloy film watch when average grain diameter be, for example, below 100nm, the maximum rough surface of aluminium alloy film Degree Rmax is below 60nm.The containing ratio of the nitrogen that aluminium alloy film is included be, for example, more than 0.5 mass % and 5.7 mass % with Under.It is preferred that the difference of the standard electrode potential of the standard electrode potential and aluminium of the metallic element beyond the aluminium that included of aluminium alloy film Absolute value is below 0.64V, and the containing ratio of the metallic element in aluminium alloy film is more than 1.0 mass % and below 1.9 mass %. Metallic element is, for example, Ti or Nd.But, the standard electrode potential of metallic element not limited to this, or metallic element with The absolute value of the difference of the standard electrode potential of aluminium is other metallic elements (for example, Mn, Mg, Zr, V and Pb) of below 0.64V.And And, metallic element can also be Mo, Nb or Hf.Aluminium alloy film can also include these metallic elements of more than two kinds.Aluminium alloy Film is for example formed by DC magnetron sputtering methods.It is preferred that the thickness of aluminium alloy film be also at about more than 500nm and about 1500nm with Under scope, e.g. about 1 μm.

Then, as shown in Fig. 4 (b), anodic oxidation is carried out by the surface 18s to aluminium film 18, is formed and there are multiple recesses The porous anode layer (porous alumina layer) 14 of (pore) 14Ap.Porous alumina layer 14 has：With recess 14Ap's Porous layer；And barrier layer (bottom of recess (pore) 14Ap).The interval (distance between centers) of known adjacent recess 14Ap Equivalent to substantially 2 times of the thickness on barrier layer, substantially it is directly proportional to voltage during anodic oxidation.This relation is for Fig. 4 (e) institutes The final porous alumina layer 14 for showing also is set up.

Porous alumina layer 14 is for example formed by surface 18s carrying out anodic oxidation in acid electrolyte.Shape The electrolyte used in operation into porous alumina layer 14 e.g. include from including oxalic acid, tartaric acid, phosphoric acid, sulfuric acid, The aqueous acid selected in chromic acid, citric acid, the group of malic acid.For example, by using the oxalic acid aqueous solution (matter of concentration 0.3 Amount %, 10 DEG C of liquid temperature), with the anodic oxidation that applied voltage 80V carries out 55 seconds to the surface 18s of aluminium film 18, form porous oxygen Change aluminium lamination 14.

Then, as shown in Fig. 4 (c), by making the etchant of the catalytic oxidation aluminium of porous alumina layer 14 regulation is etched Amount, thus, the opening portion for making recess 14Ap expands.Because the opening portion of recess 14Ap expands, two-dimentional size Dp of recess 14Ap Become big.If two-dimentional size Dp of recess 14Ap is equal with adjacent space D int of recess 14Ap, can be in adjacent recess 14Ap Between formed jut 15.By the species, concentration and the etching period that adjust etching solution, etch quantity (that is, recess 14Ap can be controlled Size, depth and jut 15 top size).As etching solution, can using such as phosphoric acid of 10 mass %, formic acid, The organic acids such as acetic acid, citric acid, sulphur aqueous acid, chromic acid phosphoric acid mixed aqueous solution.For example, using phosphate aqueous solution (10 matter Amount %, 30 DEG C) carry out the etching of 20 minutes.

Afterwards, as shown in Fig. 4 (d), can pass through partly to carry out anodic oxidation to aluminium film 18 again, make recess 14Ap exist Depth direction grows and makes porous alumina layer 14 thickening.Here, the growth of recess 14Ap is from the recess for having been formed The bottom of 14Ap starts, therefore, the side of recess 14Ap becomes step-like.

After this, moreover it is possible to as needed, further entered by making the etchant of the catalytic oxidation aluminium of porous alumina layer 14 Row etching, thus, the aperture for making recess 14Ap further expands.As etching solution, here it is also preferred that using above-mentioned etching solution, As long as actually being bathed using same etch.

So, above-mentioned anodic oxidation operation and etching work procedure are alternately repeated a number of times, shown in such as Fig. 4 (e), can be obtained To the hardware 100A on surface with jut 15.In hardware 100A, two-dimentional size Dp of recess 14Ap with it is recessed Adjacent space D int of portion 14Ap is equal.

(the thickness t of porous alumina layer 14 shown in Fig. 4 (e)_p) there is porous layer (the depth Dd phase of thickness and recess 14Ap When) and barrier layer (thickness t_b).The thickness t of porous alumina layer 14_pE.g., from about it is less than 1 μm.What porous alumina layer 14 had Recess 14Ap for example can be cone, and with step-like side.As described above, the adjacent space D int phase of recess 14Ap When in the thickness t on barrier layer_bSubstantially 2 times.

Additionally, under the porous alumina layer 14 shown in Fig. 4 (e), there is the not anodized metal in aluminium film 18 Remaining layer (aluminium remaining layer) 18r.As needed, in order to there is no aluminium remaining layer 18r, it is also possible to substantially aluminium film 18 is entered completely Row anodic oxidation.For example, in the case where inorganic material layer 16 is thin, easily induced current can be supplied from the side of aluminium base 12.

The manufacture method of the hardware gone out in this example can manufacture the counnter attack for making described in patent document 2～4 Penetrate the mould of film.It is preferred that the antireflection film that the display floater of high-resolution is used has the sharp convex portion in top.Thus, it is preferable to In manufacture method for the mould for making antireflection film, by be alternately repeated a number of times above-mentioned anodic oxidation operation and Etching work procedure (such as 5 times：5 anodic oxidations and 4 etchings) and terminated with anodic oxidation operation, make the bottom of recess 14Ap into For point.

On the other hand and, the bactericidal action of hardware does not require that the bottom of recess 14Ap is a little, therefore to simplify above-mentioned The manufacture method of mould.The manufacturing process of such as hardware both can be terminated with anodic oxidation operation, it is also possible to etch work Sequence terminates.Hardware 100A can also be manufactured by respectively carrying out 1 anodic oxidation operation and etching work procedure respectively.Such as Fig. 4 E exemplified by (), the bottom of recess 14Ap can be a little.The bottom not limited to this of recess 14Ap, it is also possible to band circularity.Recess The bottom of 14Ap can also be flat, i.e. the shape of recess 14Ap can also be the substantially frustum of a cone.

But, in order to form jut 15,1 etching work procedure is preferably at least carried out.Its reason is, the two dimension of recess 14Ap Size Dp can be extended by etching work procedure.Operation can also be suitably etched until two-dimentional size Dp of such as recess 14Ap Till equal with adjacent space D int of recess 14Ap.

By alternately anodic oxidation operation and etching work procedure, the side of recess 14Ap for example can be relative to the method on surface Line direction inclines.At least a portion of the side of recess 14Ap for example can be step-like.

There is excellent bactericidal action to make hardware, it is believed that the top of more preferably jut 15 is a little.Can also be After forming recess 14Ap, anodic oxidation operation and/or etching work procedure are suitably repeated, until between adjacent recess 14Ap Till the top of jut 15 becomes a little.For example, when the opening portion of the substantially recess 14Ap of cone shape is extended, recess The part final residue farthest from center 14o of the bottom surface of 14Ap and pointed projections 14c can be formed.

Hardware 100A can also be entered to exercise as needed after hardware 100A is obtained by above-mentioned manufacturing process Surface-stable process (such as be heat-treated).Stabilization processes can not be carried out with carrying out sealing of hole to recess 14Ap.For example can be by Hardware 100A is put into baking box and is heat-treated, so that the surface-stable of hardware 100A.

The hardware that stabilization processes are not carried out for example changes colour sometimes after certain hour is contacted with water.Hardware Sometimes can also change colour and become transparent.This discoloration (including transparence) can confirm by visual observation.Think due to hardware The shape of moth ocular structure of reversion on surface there occurs change, so the surface of hardware there occurs discoloration.If carrying out steady Determining process, then can prevent the change of the shape of the moth ocular structure of the discoloration of hardware and the reversion on surface.For example, as below Experimental example is shown like that, with more than 100 DEG C and less than 250 DEG C of the baking box hardware that carried out being heat-treated for 3 hours with water Still without discoloration after contacting 49 hours.With reference to the specific condition of the aftermentioned stabilization processes of experimental example.

Hardware 100B shown in Fig. 1 (b) also can be for example, by making above-mentioned anodic oxidation operation combine with etching work procedure To manufacture.The manufacture method of hardware 100B is illustrated with reference to Fig. 5 (a)～(c).

First, with same with reference to illustrated by Fig. 4 (a) and (b), preparation mould base material 10, by the surface to aluminium film 18 18s carries out anodic oxidation, forms the porous alumina layer 14 with multiple recesses (pore) 14Bp.

Then, as shown in Fig. 5 (a), by making the etchant of the catalytic oxidation aluminium of porous alumina layer 14 regulation is etched Amount, thus, the opening portion for making recess 14Bp expands.Now, compared with the etching work procedure with reference to illustrated by Fig. 4 (c), etching is reduced Amount.That is, the size for making the opening portion of recess 14Bp diminishes.For example, 10 points are carried out using phosphate aqueous solution (10 mass %, 30 DEG C) The etching of clock.

Afterwards, as shown in Fig. 5 (b), can pass through partly to carry out anodic oxidation to aluminium film 18 again, make recess 14Bp exist Depth direction grows and makes porous alumina layer 14 thickening.Now, for example with reference to the anodic oxygen chemical industry illustrated by Fig. 4 (d) Sequence is compared, and recess 14Bp is grown deeper.For example, using oxalic acid aqueous solution (mass % of concentration 0.3,10 DEG C of liquid temperature), to apply Making alive 80V carries out the anodic oxidation (being 55 seconds in Fig. 4 (d)) of 165 seconds.

Thereafter, can with reference to same illustrated by Fig. 4 (e), by etching work procedure and anodic oxidation operation alternately repeatedly Carry out repeatedly.For example, by the way that 3 etching work procedures, 3 anodic oxidation operations are alternately repeated, shown in such as Fig. 5 (c), obtain Hardware 100B.Now, two-dimentional size Dp of recess 14Bp is less than adjacent space D int (Dp ＜ Dint).By anodic oxidation The recess 14Bp that operation and etching work procedure are formed in addition to two-dimentional size Dp is less than adjacent space D int this point, can with it is recessed Portion 14Ap is identical.The manufacturing process of recess 14Bp in addition to the etch quantity in the etching work procedure of such as Fig. 5 (a), can with it is recessed The manufacturing process of portion 14Ap is identical.

The manufacture method of the hardware 100A and 100B that go out in this example can be manufactured for making the institute of patent document 2～4 The mould of the antireflection film of record.The antireflection film requirement high uniformity that the display floater of high-resolution is used, it is therefore preferable that such as The selection of the above-mentioned material for carrying out aluminium base, the mirror finish of aluminium base, the purity of aluminium film, the control of composition, but it is sterilized Effect does not require high uniformity, accordingly, it is capable to the manufacture method of above-mentioned mould is simplified.For example, it is also possible to directly to aluminium base Surface carry out anodic oxidation.Even if in addition, the impact of the impurity for now being included due to aluminium base and define pit, finally The concaveconvex structure of the hardware for obtaining also can only produce the disorder of partial structurtes, it is believed that hardly to bactericidal action band To affect.

The hardware 100A ' and another embodiment of the invention of another embodiment of the invention are illustrated with reference to Fig. 6 Hardware 100B ' structure and manufacture method.Fig. 6 (a) represents the hardware 100A ' of another embodiment of the invention Schematic sectional view.Fig. 6 (b) represents the schematic sectional view of the hardware 100B ' of another embodiment of the invention.Figure 6 (c) is the schematic figure for illustrating the manufacture method of hardware 100A ' and hardware 100B '.

Hardware 100A ' is with the difference of hardware 100A, by the Metal Substrate to example in Fig. 6 (c) The surface 18s of material 18X carries out direct anodic oxidation to manufacture.Hardware 100A ' can not prepare the mould that example goes out in Fig. 4 (a) Have base material 10 to manufacture.Hardware 100A ' is with the difference of hardware 100A, not with hardware 100A institutes Metal base 12, inorganic material layer 16 and the metal remnant layer 18r having, and there is metal base 18Xr.Hardware 100A ' Can be identical with hardware 100A in addition to above-mentioned aspect.

The manufacture method of hardware 100A ', can be with hardware in addition to preparing metal base 18X this point The manufacture method of 100A is identical.For example after metal base 18X is prepared, use generation above-mentioned many with reference to Fig. 4 (b)～Fig. 4 (e) The condition of hole anodic oxide coating 14, so as to form recess 14Ap.Porous anode layer 14 with recess 14Ap is formed at On the metal base 18Xr of remaining, so as to obtain the hardware 100A ' shown in Fig. 6 (a).

Metal base 18X is formed by carrying out anodised metal.Metal base 18X is, for example, valve metal or stainless Steel.Metal base 18X can also include the high metal of antibacterial effect (such as golden (Au), silver-colored (Ag), platinum (Pt) or copper (Cu))。

For example can as follows manufacture hardware (for example being formed by the aluminium) 100A ' with regularly arranged recess.It is preferred that Systematicness for making the arrangement of the recess of the mould of the antireflection film described in patent document 2～4 is low, using porous sun The concaveconvex structure of pole oxide layer it is bactericidal in the case of, it is believed that the systematicness of the arrangement of recess be do not have it is influential.

Following operation is carried out after aluminium base 18X is prepared.As long as example forming the porous oxidation that thickness is for about 10 μm After aluminium lamination, the porous alumina layer for being generated is removed by etching, then, to generate the condition of above-mentioned porous alumina layer Carry out anodic oxidation.Thickness is that 10 μm of porous alumina layer can be formed by making anodizing time elongated.Work as life Into the thick porous alumina layer of this comparison, and when the porous alumina layer is removed, aluminium film or aluminium base can not be present in Concavo-convex, processing strain impact caused by the particle on the surface of material, and form the Woelm Alumina with regularly arranged recess Layer.Additionally, the removing of porous alumina layer preferably uses the mixed liquor of chromic acid and phosphoric acid.When being etched for a long time, have When galvanic corrosion can occur, but chromic acid has the effect for suppressing galvanic corrosion with the mixed liquor of phosphoric acid.

Hardware 100B ' shown in Fig. 6 (b) is with the difference of hardware 100A ', porous anode layer The concaveconvex structure on 14 surface includes multiple recess 14Bp.Hardware 100B ', can be with gold in addition to multiple recess 14Bp Metal elements 100A ' is identical.The manufacturing process of hardware 100B ' in addition to forming the operation of multiple recess 14Bp, Ke Yiyu Hardware 100A ' is identical.

The manufacture method of hardware 100B and hardware 100B ' is not limited to said method.Work can not also be etched Sequence and hardware 100B and hardware 100B ' are only manufactured by anodic oxidation operation (referring for example to the described later 5th examination Sample).In this case, the shape of recess 14Bp can be for example substantially cylindric.The side of recess 14Bp can be with surface Normal direction is almost parallel.

Hereinafter, the hardware for illustrating experimental example explanation embodiments of the present invention has bactericidal properties.

In order to make each sample, tantalum oxide layers and aluminium alloy layer (Al-Ti layers) film forming are made successively on a glass.Alternately Above-mentioned anodic oxidation operation and etching work procedure (5 anodic oxidation operations, 4 etching work procedures) are carried out, table is made on a glass Face has the porous alumina layer of the moth ocular structure of reversion, so as to obtain the 1st sample.

2nd sample is by pair giving obtained from releasing agent with the surface of the 1st sample identical sample.Releasing agent is used The OPTOOL DSX of Daikin Ind Ltd's manufacture.After releasing agent is given in the way of flowing down from top, by rotation Device rotates sample, so that releasing agent is spread evenly on glass plate.

3rd sample and the 4th sample are to give silane coupler S1 by the surface respectively pair with the 1st sample identical sample With obtained from silane coupler S2.Silane coupler S1 is the KBM-1403 of Shin-Etsu Chemial Co., Ltd's manufacture, is not wrapped Containing amino.Silane coupler S2 is the KBM-603 of Shin-Etsu Chemial Co., Ltd's manufacture, comprising amino.Silane coupler S1 Represented with following chemical formula (structural formula) (1) and (2) respectively with silane coupler S2.

[chemical formula 1]

(CH₃O)₃SiC₃H₆NHC₂H₄NH₂ (2)

Silane coupler S1 and S2 have used stoste.With regard to the 3rd sample and the 4th sample, also silane is being imparted to surface After coupling agent, by circulator sample is rotated.

With regard to the 2nd～the 4th sample, observe to confirm the table of porous alumina layer by scanning electron microscope (SEM) The moth ocular structure of the reversion in face is not demolded agent or silane coupler is buried.Fig. 7 (a) represents the table that the 3rd sample is observed with SEM The SEM pictures in face, Fig. 7 (b) represents the SEM pictures in the section that the 3rd sample is observed with SEM.As shown in Fig. 7 (a) and Fig. 7 (b), can confirm that Recess is not buried.Other samples are similarly confirmed.

The contact angle of water and hexadecane at 22 DEG C to each Specimen Determination.(the consonance of the contact angle meter used in measure Interface science company system, PCA-1).The mean value of the contact angle for determining 5 times is illustrated in table 1 below.

[table 1]

Numbering	The material that surface is given	The contact angle [°] of water	The contact angle [°] of hexadecane
				1	Nothing	109.4	29.3
2	Releasing agent	137.2	110.4
				3	Silane coupler S1	106.7	26.7
4	Silane coupler S2	53.6	22.7

Bactericidal evaluation has been carried out by below step.

1. the bacterium diluent A that bacterium number is 1E+05CFU/mL magnitudes has been prepared '.If to bacterium diluent A ' in bacterium number carry out Count, be then 4.2E+05CFU/mL.

2. as nutrient source by 1/500NB culture mediums (with aqua sterilisa by NB culture mediums (Eiken Chemical manufacture, Broth medium E-MC35) it is diluted to 500 times) it is added to 1. bacterium diluent A ' (following the 5.4a of JIS2801)).Will The bacterium dilution is used as bacterium diluent A.

3. bacterium diluent A is respectively dripped 400 μ L to the respective surface of the 1st～the 4th sample, closed the lid.

4. the 1st～the 4th sample is respectively put into transparent vessel.In a reservoir, in order to prevent drying, being also put into drip has The absorbent cotton of the aqua sterilisa of 400 μ L.

5. in order to investigate the result after 3 kinds of times (0.1 hour, 4 hours and 24 hours), by the of above-mentioned 3. and 4. The group of the 1～the 4th sample has made 3 groups.

6. the group of the sample of the result by investigation behind 4 hours and 24 hours is respectively put into big container.In big appearance In device, in order to further prevent drying, the beaker of the aqua sterilisa equipped with 150mL and the water suction of the aqua sterilisa containing 40mL are also put into Paper.The lid of big container is covered, is cultivated by the time of respective regulation at 35 DEG C.

7., after the time (0.1 hour, 4 hours and 24 hours) for specifying, the flushing of bacterium has been carried out.Add to filter bag The aqua sterilisa of 9.6mL is added.Filter bag is put into together with cover with sample, has been sufficiently carried out rubbing and has been washed.The bacterium solution is dilute as bacterium Release liquid B.

8. bacterium dilution B is diluted with aqua sterilisa.The bacterium dilution that bacterium dilution B is diluted into 10 times is used as bacterium dilution C, bacterium dilution B is diluted to 100 times of bacterium dilution as bacterium dilution D.

9. bacterium dilution is spilt to Pei Telei films (ペトリ Off イ Le Si), cultivated 2 days with 35 DEG C, in bacterium dilution B Bacterium number is counted.Spilling to the bacterium dilution of Pei Telei films is respectively, is being that bacterium dilution C1mL and bacterium are dilute after 0.1 hour Liquid D1mL is released, had been bacterium dilution C1mL and bacterium dilution D1mL after 4 hours, be bacterium dilution after 24 hours B1mL, bacterium dilution C1mL and bacterium dilution D1mL.

Result is illustrated in table 2 below and Fig. 8.Fig. 8 is to represent the bacterium in the bacterium dilution B relative to the elapsed time (h) The coordinate diagram of number (CFU/mL).Additionally, in fig. 8, for the ease of viewing, in the case where bacterium number is 0, carry out as 0.01 Draw.

[table 2]

Elapsed time [h]	0.1	4	24
				1st [CFU/mL]	430	100	0
2nd [CFU/mL]	1720	240	43
				3rd [CFU/mL]	750	130	0
4th [CFU/mL]	50	0	0

Bacterium dilution B is that bacterium diluent A (bacterium number is the magnitude of 1E+05CFU/mL) is diluted to obtained from 25 times, because If this sample does not have bactericidal effect, bacterium number should be the magnitude of 1E+04CFU/mL.That is, due to bacterium diluent A ' in bacterium number it is former Come for 4.2E+05CFU/mL, if result, it is believed that sample does not have bactericidal effect, the bacterium number in bacterium dilution B is about 1.7E+ 04CFU/mL。

Knowable to table 2 and Fig. 8, in all the 1st～the 4th samples, bacterium number is reduced, and bactericidal action is confirmed that.It is special It is not that the 1st sample, the 3rd sample and the 4th sample have just been reduced in the bacterium number after 0.1 hour, it is taken as that bactericidal action is present Quick-acting.In addition, the 4th sample reduces by 2 digits in the bacterium number after 0.1 hour, in the bacterium number vanishing after 4 hours.Think The bactericidal effect of the 4th sample is especially high.

1st sample and the 3rd sample are identical in the magnitude of the bacterium number in each elapsed time.As shown in Table 1 above, the 1st sample It is respectively close value with the value to water and the contact angle of hexadecane of the 3rd sample.The reason for result of bactericidal effect is close can Can be that the 1st sample and the 3rd sample have identical water proofing property and lipophile.

It is the ammonia included by silane coupler S2 to be additionally considered that the 4th sample has the bactericidal action more excellent than the 3rd sample Caused by base.

It is excellent to have hardware it can be seen from the result of the contact angle shown in above-mentioned table 1 and the result of above-mentioned table 2 Bactericidal properties, be less than 110.4 ° preferably for example to the contact angle of hexadecane.More preferably be to the contact angle of hexadecane 29.3 ° with Under.

Then, bactericidal properties are evaluated for the 5th～the 7th sample.

5th sample using with the 1st sample identical material formed.But, be not etched operation and only pass through into 1 anodic oxidation operation of row, defines the concaveconvex structure on surface.

6th sample is with making with the 1st sample identical material and identical method.It is as shown in table 3 below, to water and ten The contact angle of six alkane shows the value roughly the same with the 1st sample.

7th sample is the PET film that surface does not have concaveconvex structure.Surface treatment is not given to the surface of the 5th～the 7th sample Agent.

The SEM pictures that the surface of the 5th sample and the 6th sample is observed with SEM are illustrated in Fig. 9 (a) and Fig. 9 (b).Fig. 9 A () and Fig. 9 (b) are respectively to observe the 5th sample and the 6th sample with the angle that 45 ° have been inclined from normal to a surface direction with SEM Surface SEM pictures.Such as can be seen that on the surface of the 6th sample according to Fig. 9 (b), it is (black in SEM pictures in adjacent recess Part) between be formed with jut.And on the other hand, understood according to Fig. 9 (a), do not form projection on the surface of the 5th sample Portion.There is generally flat face or gentle curve between the recess (the black part in SEM pictures) on surface.

With method same as described above the surface of each sample is determined to water and the contact angle of hexadecane.By result in table 3 In illustrate.

[table 3]

Numbering	The material that surface is given	The contact angle [°] of water	The contact angle [°] of hexadecane
				5	Nothing	13.9	7.1
6	Nothing	109.6	29.4
				7	Nothing	61.0	9.0

The bactericidal evaluation of the 5th～the 7th sample is substantially the same with the step of explanation in above-mentioned table 2.Wherein, investigate Elapsed time be set to 0.05 hour, 3 hours, 6 hours and 24 hours this 4 kinds.In addition, bacterium diluent A ' in bacterium number be originally 1.1E+05CFU/mL.It is thus regarded that, if sample does not have bactericidal effect, bacterium dilution obtained from bacterium diluent A is set into 25 times Bacterium number in liquid B substantially 4.4E+03CFU/mL.

Result is illustrated in table 4 below and Fig. 9 (c).Fig. 9 (c) is to represent to be tried relative to the 5th～the 7th of the elapsed time (h) The coordinate diagram of the bacterium number (CFU/mL) in the bacterium dilution B of sample.Additionally, being 0 in bacterium number for the ease of viewing in Fig. 9 (c) In the case of, drawn as 1.

[table 4]

Elapsed time [h]	0.05	3	6	24
					5th [CFU/mL]	4000	1900	80	44
6th [CFU/mL]	5400	460	310	0
					7th [CFU/mL]	6200	6650	12500	53200

Such as can be seen that the bactericidal action in the 5th sample and the 6th sample from table 4 and Fig. 9 (c) can be confirmed.Especially It is that the 6th sample has the bactericidal properties more excellent than the 5th sample.5th sample and the 6th sample to surface do not give any material, because The physical arrangement on this only surface is different.In the case where the physical arrangement on surface is only compared, it is thus identified that as the 6th sample In the case of with jut, there is more excellent bactericidal action compared with it there is no jut as the 5th sample. 7th sample (PET) does not have bactericidal action, bacterium number process over time and increase.

Then, bactericidal properties are evaluated for the 8th sample and the 9th sample.

8th sample is with making with the 4th sample identical material and identical method.It is as shown in table 5 below, to water and ten The contact angle of six alkane shows the value roughly the same with the 4th sample.

9th sample is to apply silane coupler S2 (with the phase used in the 4th sample by the surface to glass blank Obtained from together).

With method same as described above the surface of the 8th and the 9th sample is determined to water and the contact angle of hexadecane.By result Illustrate in table 5.

[table 5]

Numbering	The material that surface is given	The contact angle [°] of water	The contact angle [°] of hexadecane
				8	Silane coupler S2	53.7	22.8
9	Silane coupler S2	51.3	7.8

The bactericidal evaluation of the 8th and the 9th sample is substantially the same with the step of explanation in above-mentioned table 2.Wherein, investigate Elapsed time be set to 0.08 hour, 0.5 hour, 1 hour, 3 hours and 24 hours this 5 kinds.In addition, bacterium diluent A ' in bacterium Number was 2.6E+05CFU/mL originally.It is thus regarded that, if sample does not have bactericidal effect, bacterium diluent A is set into 25 times and is obtained Bacterium dilution B in bacterium number substantially 1.0E+04CFU/mL.

Result is illustrated in table 6 below and Fig. 9 (d).Fig. 9 (d) is to represent to be tried relative to the 8th and the 9th of the elapsed time (h) The coordinate diagram of the bacterium number (CFU/mL) in the bacterium dilution B of sample.Additionally, being 0 in bacterium number for the ease of viewing in Fig. 9 (d) In the case of, drawn as 0.1.

[table 6]

Elapsed time [h]	0.08	0.5	1	3	24
						8th [CFU/mL]	5440	1860	1840	0	0
9th [CFU/mL]	8800	5800	6300	900	0

Such as can be seen that the bactericidal action in the 8th sample and the 9th sample according to table 6 and Fig. 9 (d) can be confirmed.It is special It is not that the 8th sample has the bactericidal properties more excellent than the 9th sample.Understand that the 8th sample is assigned due to the physical arrangement on surface and to surface The silane coupler S2 that gives and there are especially excellent bactericidal properties.

Next, effect of the investigation to the stabilization processes of the hardware enforcement of embodiments of the present invention.

Prepare 3 with the sample made with the 1st sample identical material and identical method, by each different condition realities Stabilization processes (here is heat treatment) are applied so as to obtain the 10th～the 12nd sample.Specifically, by the 10th～the 12nd sample After being put into the baking box before heating, heating oven is until reach the temperature of regulation.The temperature of regulation is referred to, in the case of the 10th sample For 250 DEG C, it in the case of 120 DEG C, the 12nd sample is 100 DEG C to be in the case of the 11st sample.It is certainly when in sample input baking box The state (that is, the surface of sample is dry) being so dried.3 hours temperature are kept after the temperature for reaching respective regulation, so The power supply of baking box is cut off afterwards.After baking box becomes normal temperature, sample is taken out from baking box.

After stabilization processes are implemented, in the 10th～the 12nd sample discoloration is not seen.It is thus regarded that, by stable Change is processed, and the shape of the moth ocular structure of the reversion that sample has on surface does not change.

13rd sample is, with the sample made with the 1st sample identical material and identical method, not implement to stabilize Process.The thickness t of the porous alumina layer 14 of the 10th～the 13rd sample_p(with reference to Fig. 4 (e)) is 100nm～300nm.

Drip 400 μ L pure water to the respective surface of the 10th～the 13rd sample, close the lid.By the 10th～the 13rd sample point Transparent vessel is not put into, is put into 37 DEG C of thermostat.For each sample, through regulation time (3 hours, 6 hours, 21 Hour, 49 hours, 120 hours and 144 hours) after whether changed colour with visually observing and having investigated.

Result is illustrated in table 7 below.

[table 7]

Elapsed time [h]

3

6

21

49

120

144

10th

○

11st

○

12nd

○

×

13rd

○

×

In table 7, "○" represents and do not change colour that "×" indicates discoloration."×" also includes being connect with the pure water in sample Tactile position becomes transparent situation.The position of transparence after the test with air contact in the state of place when, can also sometimes It is changed into black.Figure 10 illustrates the SEM pictures on the surface for becoming transparent position observed in the 13rd sample with SEM.According to figure 10 understand, become transparent position in hardware, the shape of the moth ocular structure of the reversion on surface there occurs change.

It can be seen from table 7, the 13rd sample that stabilization processes are not carried out sees discoloration when through 49 hours.With 100 The 12nd sample for DEG C implementing stabilization processes sees discoloration when through 120 hours.Implemented with 120 DEG C and 250 DEG C steady 11st and the 10th sample of fixedization process was not seeing yet discoloration after 144 hours.

In order to be compared, the sample made using anodic oxidation operation and etching work procedure is not carried out completely carried out with Above-mentioned 10th～the 13rd sample identical experiment.In this case, in full terms (at the presence or absence of stabilization processes, stabilisation The temperature of reason, elapsed time) under do not see discoloration.

With regard to the mechanism of the discoloration of hardware, the present inventor is as follows to be investigated.

The discoloration for thinking hardware is to there occurs change by the shape of the moth ocular structure of the reversion on the surface of hardware Caused.Applicant of the present invention has found the thickness t according to porous alumina layer 14_pAnd/or the difference of the shape of recess 14Ap, Sometimes porous alumina layer 14 appears as different colors (that is, reflected light looks coloring), and by the result systematically investigated Disclosed in International Publication No. 2011/145625.In order to refer to, International Publication No. 2011/ is quoted in this manual The complete disclosure of No. 145625.Think hardware discoloration be, for example, by porous alumina layer 14 at least a portion with Water reacts, and forms hydroxide calorize aluminium (Al (OH)₃) or aluminum oxide (Al₂O₃·nH₂) or its hydrate (Al O₂O₃· nH₂O), the thickness t of porous alumina layer 14_pAnd/or the shape of recess 14Ap there occurs caused by change.Think hardware Discoloration be by with used in the sealing pores of porous anode layer hydration reaction identical reaction cause.

Furthermore, it is believed that be not only porous alumina layer 14 react with water, the aluminium remaining layer under porous alumina layer 14 18r also reacts with water or acid, becomes hydroxide calorize aluminium or aluminum oxide or its hydrate, so as to cause hardware to become Transparent.It was found by the inventors of the present invention that in partly certain sample of discoloration and transparence, becoming transparent position and not having The position for having discoloration is compared, substantially thick 3 μm.Think the position of transparence due to forming above-mentioned oxide or hydroxide calorize Thing, thus it is thicker than other parts.

It is in general, many as the process of the surface stabilization for making porous anode layer (such as porous alumina layer) Well known is sealing pores.By the porous alumina layer of anodic oxidation formation, corrosion resistance is bad under its former state state, But can obtain excellent corrosion resistance by implementing sealing pores.For example by processing porous oxidation in high-temperature pressurizing vapor Aluminium boils Woelm Alumina to carry out sealing pores in the pure water of boiling.Think when sealing pores are carried out, porous A part for alumina layer can occur hydration reaction, so as to pore (recess) is sealed up or narrowing.Carry out more at high temperature Sealing pores are preferred.

The stabilization processes that the hardware of embodiments of the present invention is implemented are different from the following areas commonly known Sealing pores.Stabilization processes be sealing of hole is not carried out to pore (recess) 14Ap of porous alumina layer 14 in the case of carry out 's.It is preferred that carrying out stabilization processes in the case where the shape of moth ocular structure of the reversion that surface has is not changed.By this Stabilization processes, improve metal structure while impact can not be brought on the bactericidal effect that the hardware of embodiments of the present invention has The corrosion resistance of part.It is preferred that for example carrying out stabilization processes (such as being heat-treated) to dry hardware.

According to the result of table 7, the temperature of preferred stabilization processes (being for example heat-treated) is, for example, more than 100 DEG C.More preferably The temperature of heat treatment is, for example, more than 120 DEG C.The time of heat treatment is, for example, 3 hours.

In general, when the metal after to processing is heat-treated (annealing), can produce be referred to as recovering, recrystallize and 3 processes of grain growth.When the temperature of the metal after processing is gradually increasing, occur first at relatively low temperatures extensive It is multiple.In recovery process, the lattice defect (such as point defect or dislocation) produced in crystallization by plastic deformation is disappeared.When When improving temperature, deformation-free new crystal grain (recrystallization) can be formed, when temperature is further improved, crystal grain can be further larger Ground generates (grain growth).For example for aluminium, recovery is occurred below at substantially 200 DEG C, more than substantially 200 DEG C and 350 DEG C Recrystallization is occurred below, grain growth occurs more than substantially 350 DEG C.

In order to not make the change in shape of the moth ocular structure of the reversion of porous alumina layer 14, the embodiment party of the preferred pair present invention The stabilization processes that the hardware of formula is implemented do not make the size variation of crystal grain, i.e., grain growth does not occur.In addition, more preferably Do not recrystallize.Thus, such as preferably less than 350 DEG C of the temperature of stabilization processes (heat treatment), more preferably 250 DEG C with Under.In addition, when treatment temperature is high, the metal base 12,18Xr for supporting porous alumina layer 14 is possible to deformation.In addition, from From the viewpoint of suppressing consumption electric power, it is also preferred that treatment temperature is low.From the point of view of this viewpoint, preferred stabilization processes (heat treatment) E.g., less than 150 DEG C of temperature.

From experimental example as can be seen that being implemented at stabilisation by the surface of the hardware to embodiments of the present invention Reason, even if hardware contacts certain hour with water, can also suppress the moth ocular structure of the discoloration of hardware and the reversion on surface Shape change.Thus, the bactericidal effect with the change of the shape of surface texture can be suppressed to reduce.The embodiment party of the present invention The hardware of formula can also meet the demand of the bactericidal action (including mould proof effect) in the environment of such as high temperature and humidity.This The hardware of bright embodiment will not also lose its sterilization effect by implementing stabilization processes in the environment of high temperature and humidity Really, it is suitable for this changing commanders.In addition, the hardware of embodiments of the present invention can be pressed down by implementing stabilization processes Make its outward appearance to change.Thus, the hardware of embodiments of the present invention passes through to implement stabilization processes, for example aftermentioned Interior decoration building materials in its appearance design be also not damaged, and be suitable for interior decoration building materials.

Both can also can carry out after being processed by surface conditioning agent before processing is carried out by surface conditioning agent Stabilization processes.

(embodiment 1)

The hardware of embodiments of the present invention is for example suitable for heat exchanger.Embodiments of the present invention 1 are tools The heat exchanger of the hardware of standby embodiments of the present invention.Possess what is formed by the hardware of embodiments of the present invention Fin, so as to obtain the heat exchanger with bactericidal action.May adhere in air on the fin of heat exchanger Condensate moisture so as to generate water.The heat exchanger of embodiments of the present invention can suppress to be led by the water droplet for being attached to fin The generation of the mould of cause.Additionally, the heat exchanger of embodiments of the present invention 1 is not limited to the heat exchanger of the example below.

It is another with the present invention with reference to the heat exchanger 200A of Figure 11 (a)～Figure 11 (c) explanation embodiments of the present invention The heat exchanger 200B of embodiment.Figure 11 (a) is showing for the fin 50 that the heat exchanger of embodiments of the present invention 1 has Meaning property sectional view.Figure 11 (b) and Figure 11 (c) are respectively the heat exchanger 200A and heat exchanger 200B of embodiments of the present invention Schematic sectional view.

As shown in Figure 11 (a), fin 50 is for example formed by hardware 100A '.Fin 50 has metal base 18Xr and the porous anode layer 14 being formed on metal base 18Xr.The surface of porous anode layer 14 has sub-micron The concaveconvex structure of magnitude.Concaveconvex structure includes that from normal to a surface direction two-dimentional size when watching is more than 100nm and is less than Multiple recess 14Ap of 500nm.Fin 50 have with hardware 100A ' identical surface textures (including physical arrangement and Chemical property).

As shown in Figure 11 (b), heat exchanger 200A has fin 50.Fin 50 possesses the table of bactericidal action Face, therefore heat exchanger 200A can have bactericidal effect.

The fin 50 of heat exchanger 200A is not limited to hardware 100A ', can be by above-mentioned embodiment party of the invention Any one formation in the hardware of formula.

Heat exchanger 200A for example also has pipe 60.For example, pipe 60 is full of by cold-producing medium, in cold-producing medium and heat exchanger The exchange of heat energy is carried out between gas or liquid in 200A.The exchange of heat energy is carried out via fin 50.In order to improve heat The exchange efficiency of energy, the surface area of preferred fin 50 is big.Heat exchanger 200A as shown in Figure 11 (b), such as big The fin 50 of wave mode is configured between the pipe 60 for causing configured in parallel.Or, it is also possible to the heat exchanger as shown in Figure 11 (c) Pipe 60 like that, wave mode is configured in the way of the fin 50 of the almost parallel configuration of insertion by 200B.Heat exchanger 200B except Beyond the configuration of fin 50 and pipe 60, can be identical with heat exchanger 200A.

The heat exchanger of embodiments of the present invention 1 can for example be used for air-conditioning (air conditioner), refrigerator or freezer.It is empty Stealthily substitute and include room conditioning and on-board air conditioner.In the heat exchanger of embodiments of the present invention 1, the surface of fin has sterilization Property, therefore can suppress by the generation for being attached to mould caused by the water droplet of fin.Can also have to the liquid in heat exchanger Or the bactericidal action of gas.In the heat exchanger of embodiments of the present invention 1, the surface of fin has sub-micrometer scale Concaveconvex structure, therefore the surface area of fin becomes big, can improve heat exchanger effectiveness.

It is above-mentioned to patent document 5 discloses that the heat exchange that there is the pore formed by anodic oxidation on the surface of fin Device.The heat exchanger of patent document 5 has pore on the surface of fin, thus achieves the raising of drainage performance.In patent In the heat exchanger of document 5, the pore of fin is not formed by being etched operation by anodic oxidation operation, Therefore jut will not be formed between adjacent pore.

The heat exchanger of embodiments of the present invention 1 only just can have bactericidal action by the physical arrangement of fin.Cause And, can not make cost and/or manufacturing process that there is bactericidal action with increasing.And, as described above, by the surface to fin Surface conditioning agent (such as releasing agent or coupling agent) is given, bactericidal action is can further improve.

The metal base that fin has for example is formed by valve metal.The porous anode layer that fin has for example leads to Cross carries out anodic oxidation and is formed to valve metal.As the metal for forming hardware and/or porous anode layer, can make Use stainless steel.The metal base that fin has is, for example, aluminium base, and the porous anode layer that fin has is, for example, many Porous aluminum oxide layer.Aluminium has for example light, low cost, thermal conductivity is excellent, the feature that can be easily worked, therefore is used for radiating Piece.

In the case where the porous anode layer of fin is formed by carrying out anodic oxidation to titanium, titanium oxide is light Catalytic active substance, therefore by fin irradiation light (such as ultraviolet), also obtaining based on light-catalysed bactericidal effect. Can further improve the bactericidal effect of heat exchanger.The air-conditioning that for example can be irradiated in the light for indoor fluorescent lamp sets In the case of being placed in off-premises station that outdoor and sunshine can be irradiated to etc., without specially irradiation light (such as ultraviolet), just having can Can obtain based on light-catalysed bactericidal effect.

Then, radiator (low-temperature receiver) 210A and Ben Fa of embodiments of the present invention is illustrated with reference to Figure 12 (a)～Figure 12 (f) The radiator 210B of bright another embodiment.Figure 12 (a) and Figure 12 (d) are respectively the radiators of embodiments of the present invention The schematic plan of 210A and radiator 210B.Figure 12 (b) and Figure 12 (c) are respectively along the 12B-12B ' in Figure 12 (a) The sectional view of the radiator 210A of line and 12C-12C ' lines.Figure 12 (e) and Figure 12 (f) are respectively along in Figure 12 (d) The sectional view of the radiator 210B of 12E-12E ' lines and 12F-12F ' lines.

In radiator 210A and radiator 210B, fin 50 possesses the surface of bactericidal action, therefore radiator 210A and radiator 210B can have bactericidal effect.There can be bactericidal action to the gas in radiator.The surface of fin 50 Concaveconvex structure with sub-micrometer scale, therefore the surface area of fin 50 becomes big, can improve radiating efficiency.

Radiator 210A for example also has plate 70.Fin 50 is provided with plate 70.Watch in the normal direction from plate 70 When, fin 50 is, for example, the striated as exemplified by Figure 12 (a)～Figure 12 (c).Dissipating as shown in Figure 12 (d)～Figure 12 (f) Like that, when the normal direction from plate 70 is watched, fin 50 can be arranged hot device 210B by such as square lattice shape.The present invention Embodiment radiator not limited to this, the shape of fin 50 and configuration can be arbitrary.Such as fin 50 can be with It is configured to dotted line shape.For example fin 50 is configurable to checkerboard.The shape of plate 70 is also not necessarily limited to the shape for illustrating, Ke Yi By such as radiation wire configuration fin on circular plate 70.

In this manual heat exchanger includes such as radiator, evaporimeter, condenser, cooler, heater, radiator The various heat exchangers such as (low-temperature receiver), are not limited to the content of example.

The heat exchanger of such as embodiments of the present invention 1 can be used for thermantidote.Thermantidote is using the gasification of water Heat is reducing the device of the temperature of air.

(embodiment 2)

The hardware of embodiments of the present invention is for example suitable also for interior decoration building materials.Embodiments of the present invention 2 is the interior decoration building materials of the hardware for possessing embodiments of the present invention.Additionally, the interior of embodiments of the present invention 2 Decorative building material is not limited to the building materials of the example below.

The hardware of embodiments of the present invention can be used for such as door handle or handrail.By possessing with the present invention's The hardware identical surface texture (including physical arrangement and chemical property) of embodiment, so as to have bactericidal action. Door handle or handrail are due to frequently contacting with hand, therefore the organic matter of adhesive water and the nutrient source as microorganism sometimes. The interior decoration building materials of embodiments of the present invention can suppress by microorganism caused by moisture and/or organic matter (comprising mould) Produce.

The hardware of embodiments of the present invention can be used in the screen window that such as window frame is used.By possessing and this The hardware identical surface texture (including physical arrangement and chemical property) of the embodiment of invention, so as to be had The interior decoration building materials of bactericidal action.Screen window for example adheres to due to condensation sometimes water droplet, but by with bactericidal action, energy Suppress by the generation of mould caused by water droplet.

As the material of the interior decoration building materials such as door handle or screen window, for example, can be adapted to use aluminium or stainless steel.

The interior decoration building materials of present embodiment can be used for such as chair.Schematically show in fig. 13 using this enforcement The chair 60A of the interior decoration building materials manufacture of mode.

Chair 60A is for example manufactured using hardware 100A '.Chair 60A has metal base 18Xr and is formed in gold Porous anode layer 14 on category base material 18Xr.The surface of porous anode layer 14 has the concavo-convex knot of sub-micrometer scale Structure.Concaveconvex structure includes that from normal to a surface direction two-dimentional size when watching is more than 100nm and multiple recessed less than 500nm Portion 14Ap.Can be that whole chair 60A is formed, or the only part on the surface of chair 60A by hardware 100A ' (such as surface of seat 60a and backrest 60b) is formed by hardware 100A '.Chair 60A is not limited to hardware 100A ', can To be manufactured using any one in the hardware of above-mentioned embodiments of the present invention.

The shape of chair 60A is not limited to the shape for illustrating, and can be various known shapes.Can not also for example have and lean on The back of the body.

Chair 60A can be set to for example an unspecified number of chair for using.Chair 60A can be arranged at public place (example Such as station or park).Chair 60A is not limited to interior, it is also possible to be arranged at outdoor.

The purposes of the hardware of embodiments of the present invention is not limited to above-mentioned embodiment.For example can be used for daily Groceries.For example can be used for cover of the lunch box.Or, it is also possible to such as aluminum that used for kitchen appliance or stainless steel Part or pipe.Machine for kitchen use widely includes such as electric kettle, coffee machine etc..For example, it is also possible to be used for electric kettle or The pipe arranged between the internal container and outlet of the addition water of person's coffee machine.

Figure 14 (a) and (b) are electric heater (such as electric kettle) 70A for schematically showing embodiments of the present invention With the sectional view of 70B.

As shown in Figure 14 (a), electric heater 70A has：Container 72, it accommodates drinking water, heats accommodated drinking water； Outlet 74, it is discharged to the outside heated drinking water；And drinking-water pipe 50A (100A '), it is located at container 72 and discharges Between mouth 74.Drinking-water pipe 50A is for example formed by hardware 100A '.Drinking-water pipe 50A has metal base 18Xr and shape in inner side Into the porous anode layer 14 on metal base 18Xr.The surface of porous anode layer 14 has the recessed of sub-micrometer scale Male structure.Concaveconvex structure includes that from normal to a surface direction two-dimentional size when watching is more than 100nm and many less than 500nm Individual recess 14Ap.The surface of the inner side of drinking-water pipe 50A has with hardware 100A ' identical surface textures (including physics knot Structure and chemical property).Drinking-water pipe 50A is not limited to hardware 100A ', can be by the metal of above-mentioned embodiments of the present invention Any one formation in component.

As shown in Figure 14 (a), container 72 and/or outlet 74 can also be formed by hardware 100A '.That is, container 72 Can also have metal base 18Xr and the porous anode layer 14 being formed on metal base 18Xr in inner side.Container 72 Inner side for example includes the side and bottom surface of the inner side of container 72.Outlet 74 can also have metal base 18Xr and shape in inner side Into the porous anode layer 14 on metal base 18Xr.The inner side of outlet 74 refers to the surface with potable water contact.And And, the lid 72c of container 72 can also have metal base 18Xr with the porous sun being formed on metal base 18Xr in inner side Pole oxide layer 14.

The shape of electric heater is not limited to the shape for illustrating, and can be various known shapes.For example, such as Figure 14 (b) institutes The electric heater 70B for showing can be the type without drinking-water pipe like that.The container 72 and/or outlet 74 of electric heater 70B Can also be formed by hardware 100A '.

The detailed structure of electric heater is it is well known that therefore omitting the description.

Figure 15 is the sectional view of the beverage supply device (such as coffee machine) 80 for schematically showing embodiments of the present invention.

As shown in figure 15, beverage supply device 80 has：Container 82, it accommodates drinking water, heats accommodated drinking water；Row Outlet 84, it will be discharged including the beverage of heated drinking water to outside；And feed pipe 50B (100A '), it is located at container Between 82 and outlet 84.Feed pipe 50B is for example formed by hardware 100A '.Feed pipe 50B has metal base in inner side 18Xr and the porous anode layer 14 being formed on metal base 18Xr.The surface of porous anode layer 14 has sub-micron The concaveconvex structure of magnitude.Concaveconvex structure includes that from normal to a surface direction two-dimentional size when watching is more than 100nm and is less than Multiple recess 14Ap of 500nm.That is, the surface of the inner side of feed pipe 50B has and hardware 100A ' identical surface textures (including physical arrangement and chemical property).Feed pipe 50B is not limited to hardware 100A ', can be by above-mentioned reality of the invention Apply any one formation in the hardware of mode.

As shown in figure 15, container 82 and/or outlet 84 can also be formed by hardware 100A '.That is, container 82 also may be used So that there is metal base 18Xr and the porous anode layer 14 being formed on metal base 18Xr in inner side.The inner side of container 82 For example include the side and bottom surface of the inner side of container 82.Outlet 84 can also have metal base 18Xr and be formed in inner side Porous anode layer 14 on metal base 18Xr.The inner side of outlet 84 refers to the surface contacted with beverage.Beverage supply Device 80 can also have the beverage server system 86 of the beverage for receiving to discharge from outlet 84.Beverage server system 86 can also be by Hardware 100A ' is formed.That is, beverage server system 86 can also have metal base 18Xr and be formed in Metal Substrate in inner side Porous anode layer 14 on material 18Xr.

The shape of beverage supply device is not limited to the shape for illustrating, and can be various known shapes.Beverage supply device it is detailed Thin structure is it is well known that therefore omitting the description.

As shown in figure 16, lunch box 90a and cover of the lunch box 90b are for example manufactured using hardware 100A ' respectively.Lunch box 90a There is respectively metal base 18Xr and the porous anode layer 14 being formed on metal base 18Xr with cover of the lunch box 90b.Porous The surface of anodic oxide coating 14 has the concaveconvex structure of sub-micrometer scale.When concaveconvex structure includes from normal to a surface direction watching Two-dimentional size be multiple recess 14Ap more than 100nm and less than 500nm.That is, the surface tool of lunch box 90a and cover of the lunch box 90b Have and hardware 100A ' identical surface textures (including physical arrangement and chemical property).Lunch box 90a and cover of the lunch box 90b are equal Hardware 100A ' is not limited to, can be formed by any one in the hardware of above-mentioned embodiments of the present invention.

As shown in figure 16, lunch box 90a and cover of the lunch box 90b have concaveconvex structure in outside and inner side.It is preferred that lunch box 90a and meal Lid 90b at least has concaveconvex structure in inner side.Pass through same processes (including anodic oxidation operation on the surface of outside and inner side And etching work procedure) formed concaveconvex structure when, be respectively provided with concaveconvex structure in outside and inner side while manufacturing process can not be increased.

The shape of lunch box 90a and cover of the lunch box 90b is not limited to the shape for illustrating, and can be various known shapes.

Industrial utilizability

The heat exchanger of the fin for possessing bactericidal action with surface of embodiments of the present invention can be applicable to for example The various uses such as air-conditioning (air conditioner), refrigerator, freezer.Embodiments of the present invention with the surface for possessing bactericidal action Hardware can apply to the various uses such as interior decoration building materials or sundry goods.

Description of reference numerals

12nd, 18Xr metal bases

14 porous anode layers

14Ap, 14Bp recess

15 juts

50 fin

50A drinking-water pipes

50B feed pipes

70A, 70B electric heater

72 containers

74 outlets

80 beverage supply devices

82 containers

84 outlets

90a lunch boxes

90b covers of the lunch box

100A, 100B, 100A ', 100B ' hardwares

200A, 200B heat exchanger

210A, 210B radiator.

Claims

1. a kind of heat exchanger, it is characterised in that

With fin, above-mentioned fin has metal base and the porous anode layer being formed on above-mentioned metal base,

The surface of above-mentioned porous anode layer has the concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure is included from above-mentioned table Two-dimentional size when the normal direction in face is watched is more than 100nm and the multiple recesses less than 500nm.

2. heat exchanger according to claim 1,

Above-mentioned concaveconvex structure has the jut being formed between adjacent above-mentioned multiple recesses.

3. heat exchanger according to claim 2,

The crest line that above-mentioned jut has the side of adjacent above-mentioned multiple recesses intersecting and formed.

4. heat exchanger according to claim 1,

Above-mentioned two-dimentional size of the adjacent spacing of above-mentioned multiple recesses more than above-mentioned multiple recesses.

5. the heat exchanger according to any one of Claims 1-4,

The side of above-mentioned multiple recesses is inclined relative to above-mentioned normal to a surface direction.

6. the heat exchanger according to any one of claim 1 to 5,

At least a portion of the side of above-mentioned multiple recesses is step-like.

7. the heat exchanger according to any one of claim 1 to 6,

Above-mentioned surface is less than 110.4 ° to the static contact angle of hexadecane.

8. the heat exchanger according to any one of claim 1 to 7,

Above-mentioned surface is less than 29.3 ° to the static contact angle of hexadecane.

9. the heat exchanger according to any one of claim 1 to 8,

Above-mentioned surface was processed with surface conditioning agent.

10. heat exchanger according to claim 9,

Above-mentioned surface conditioning agent has amino.

11. heat exchangers according to any one of claim 1 to 10,

The adjacent spacing of above-mentioned multiple recesses is more than 20nm and less than 500nm.

12. heat exchangers according to any one of claim 1 to 11,

The above-mentioned two-dimentional size of above-mentioned multiple recesses is more than 140nm.

13. heat exchangers according to any one of claim 1 to 12,

Above-mentioned metal base is valve metal.

14. heat exchangers according to any one of claim 1 to 13,

Above-mentioned porous anode layer is formed by carrying out anodic oxidation to valve metal.

A kind of 15. hardwares, it is characterised in that

Possess metal base and the porous anode layer being formed on above-mentioned metal base,

The surface of above-mentioned porous anode layer has the concaveconvex structure of sub-micrometer scale, and above-mentioned surface has bactericidal effect.

16. hardwares according to claim 15,

Above-mentioned concaveconvex structure includes that from above-mentioned normal to a surface direction two-dimentional size when watching is more than 100nm and is less than Multiple recesses of 500nm.

17. hardwares according to claim 15 or 16,

18. hardwares according to any one of claim 15 to 17,

19. hardwares according to any one of claim 15 to 18,

Above-mentioned surface was processed with surface conditioning agent.

A kind of 20. methods for suppressing moulds to occur, it is characterised in that arbitrary in by making vapor and claim 1 to 14 The above-mentioned surface of the above-mentioned fin of the heat exchanger described in contacts to press down mycostatic generation.

A kind of 21. methods that sterilization is carried out to gas or liquid, it is characterised in that wanted with right by making gas or liquid The above-mentioned surface contact for seeking the above-mentioned fin of the heat exchanger described in any one of 1 to 14 comes to above-mentioned gas or liquid Carry out sterilization.

A kind of 22. methods for suppressing moulds to occur, it is characterised in that arbitrary in by making vapor and claim 15 to 19 The above-mentioned surface of the hardware described in contacts to press down mycostatic generation.

A kind of 23. methods that sterilization is carried out to gas or liquid, it is characterised in that wanted with right by making gas or liquid The above-mentioned surface for seeking the hardware described in any one of 15 to 19 contacts to carry out sterilization to above-mentioned gas or liquid.

A kind of 24. electric heaters, have：

Container, it accommodates drinking water, heats the above-mentioned drinking water for being accommodated；

Outlet, it is by heated above-mentioned drinking water to outside discharge；And

Drinking-water pipe, it is located between said vesse and above-mentioned outlet, and above-mentioned electric heater is characterised by,

Above-mentioned drinking-water pipe has metal base and the porous anode layer being formed on above-mentioned metal base in inner side, above-mentioned many The surface of hole anodic oxide coating has the concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure is included from above-mentioned normal to a surface side Two-dimentional size when viewing is the multiple recesses more than 100nm and less than 500nm.

A kind of 25. beverage supply devices, have：

Outlet, it will be discharged including the beverage of heated above-mentioned drinking water to outside；And

Feed pipe, it is located between said vesse and above-mentioned outlet, and above-mentioned beverage supply device is characterised by,

Above-mentioned feed pipe has metal base and the porous anode layer being formed on above-mentioned metal base in inner side, above-mentioned many The surface of hole anodic oxide coating has the concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure is included from above-mentioned normal to a surface side Two-dimentional size when viewing is the multiple recesses more than 100nm and less than 500nm.

A kind of 26. covers of the lunch box, it is characterised in that

With metal base and the porous anode layer being formed on above-mentioned metal base,

The surface of above-mentioned porous anode layer has the concaveconvex structure of sub-micrometer scale, and above-mentioned concaveconvex structure is included from above-mentioned table Two-dimentional size when the normal direction in face is watched is the multiple recesses more than 100nm and less than 500nm.